Electrolytic commercial production of hydrogen from hydrocarbon compounds

ABSTRACT

This invention concerns the commercial production of electrolytic hydrogen from coal and other hydrocarbon compounds. The process provides high capacity and low impedance compared to conventional diaphragm electrolytic cells. The hydrogen produced is suitable for combined cycle gas turbines and fuel cell power generation plants and for proton electrolytic membrane fuel cell powered transport vehicles.

FIELD OF INVENTION

This invention concerns an electrolytic process for the commercialproduction of hydrogen from solid, liquid, or gas hydrocarbon compoundsusing a high capacity electrolytic cell as described in U.S. Pat. No.5,882,502 Mar. 16, 1999 that functions without a diaphragm between theanode and the cathode. High capacity and low impedance of theelectrolytic cell are necessary to achieve the high capacity requiredfor the commercial production of hydrogen.

INTRODUCTION

Our way of life requires increasing energy in the form of electricityand transport energy. This must be achieved based on a reliable abundantenergy source and with acceptable pollution of the environment,particularly the production of toxic and greenhouse gases.

Coal is the most abundant and widely spread energy source of the worldwith reserves estimated to last for several hundred years. Table 1 showsthe major production of coal and the portion used in electricitygeneration. At the present, practically none is used for road transportenergy.

TABLE 1 Major Hard Coal Producers and Portion Used in ElectricityGeneration (1999) Annual Production, Used for Electricity CountryMillion Tonnes Percent PR of China 1,029 80 United States of America 91456 India 290 68 South Africa 224 90 Poland 112 96

Coal has been mainly used for power generation using the inefficientdirect coal fired steam turbine power plants or the more efficientintegrated gasification combined cycle gas turbine. Transport energy isprovided mainly by liquid hydrocarbons using inefficient internalcombustion engines. These energy systems are major causes of atmosphericpollution and there is the increasing problem of limited crude oilsupply and increasing prices.

The use of coal efficiently to supply electrical energy and transportenergy must be the centre piece of a total energy program for the comingdecades. The process as described in this invention converts coal byelectrolysis into carbon dioxide and hydrogen at a commercial ale. Thehydrogen can be used to produce electrical power by fuel cells or by thecombined cycle gas turbine. The hydrogen can also be used as fuel forfuel cell powered vehicles to replace liquid hydrocarbons such asgasoline and diesel fuel used for transport energy.

This invention applies to the conversion of solid, liquid, or gashydrocarbon compounds to hydrogen but the emphasis in the discussions iscoal electrolysis to produce hydrogen.

PRIOR ART

The electrolysis of coal has been reported since about the earlynineteen thirties but further development was probably curtailed by theuse of the diaphragm type electrolytic cell that has high impedance andlow reaction rates. The diaphragm cell would have suffered further whencoal particles and reaction by-products such as tar fouled up thediaphragm. A further handicap of the production of electrolytic hydrogenfrom coal is that one Faraday of electricity will produce only one gramof hydrogen. This makes it more important that a commercial process forthe electrolytic conversion of carbon to hydrogen must be capable ofhigh capacity.

A review of the electrolysis of coal is given by Su Moon Park in the“Electrochemistry of Carbonaceous Materials and Coal”, Journal ofElectrochemical society, 131, 363C, (1984). The following descriptionhas been obtained mostly from this publication and from a book, “FuelCells and their Applications” by Karl Kordesch and Gunther Simader, VCH,1996.

The oxidation of coal to hydrogen has been reported on since about 1932,beginning with the chemical oxidation using aqueous alkaline solutions.Subsequently, the aqueous add electrochemical oxidation of coal wasstudied. Coughlin and Farouque published a series of papers on theanodic oxidation of coal with platinum anode in sulfuric acid. Theyconcluded the following stoichiometry:

At the anode:C+2H₂O→CO₂+4H(+)+4e(−) orC+H₂O→CO+2H(+)+2e(−)At the cathode:4H(+)+4e(−)→2H₂

Coughlin's standard potential for the reaction was 0.223V vs NHE.Measurement of the ratio of H₂ to CO₂ and CO was greater thanstoichiometric indicating other reactions are occurring. Baldwin et alcarried out detailed voltametric studies on oxidation of coal in acidmedia and non-aqueous solution and suggested that the Fe(2+) ion wasresponsible for most of the oxidation in coal. The iron was leached fromthe coal. Dhoogie et al resolved the matter by carrying out detailedstudies on the mechanism of coal slurry oxidation. When coal was washedin a 1:1 sulfuric acid solution for more than 50 hours, practically noanodic current was observed. When Fe(3+) was added to the slurry and theanodic potential maintained such that Fe(2+) would be oxidised, theanodic currents were observed. Dhoogie suggested the followingmechanism:

At the anode:4Fe(3+)+Coal+2H₂O→4Fe(2+)+CO₂+4H(+)+other productsAt the anode;4Fe(2+)−4e(−)→4Fe(3+)At the cathode:4H(+)+4e(−)→2H₂

A rapid increase in reaction rate is noted for catalysts with redoxpotentials of 0.6 to 0.9 volts. This suggests that functional groups inthe coal such as the quinone and hydroquinone are responding to thecatalyst. Ce(4+) and Br(−) were the most effective electrocatalyst.

Summarizing, the fundamental mechanism of chemical coal oxidation andelectrolytic oxidation is the same; surface oxides and humic acid appearto form first and eventually, smaller hydrocarbon molecules and CO₂ areformed as oxidation proceeds. The factors that would affect theelectrolytic commercial production of hydrogen from coal are currentdensity, the type of electrolyte and its concentration, slurry density,type of catalyst in the electrolyte, nature of the coal, reagentconcentrations, size of coal particles, temperature, pressure, electrodesurface material and surface structure, and cell impedance. The currentdensity and the nature of the current application such as steady orpulsed, or a combination of both would be significant. The cellimpedance should be as low as possible to reduce energy consumption.

Carbon is the major component of coal as shown by the analysis of abituminous coal from Virginia on Table 2.

TABLE 2 Analysis of a Bituminous Coal from Virginia Proximate AnalysisComponent % by Weight Component % by Weight Moisture 2.90 Carbon, C80.31 Volatile Matter 22.05 Hydrogen, H₂ 4.47 Fixed Carbon 68.50 Sulfur,S 1.54 Ash 6.55 Oxygen, O₂ 2.85 Total 100.00 Nitrogen, N₂ 1.38 Moisture,H₂O 2.90 Ash 6.55 Total 100.00 Heating Value, Btu/Lb 14,100

As carbon is the major component of the coal by far, this thermal energycomparison will only use carbon for simplicity but it must be noted thatCoughlin and Farouque detected higher ratio than stoichiometric ofhydrogen to carbon oxides in the electrolysis of coal. Generally, thehydrogen in hydrocarbons would be converted to hydrogen ions at theanode cell and hydrogen gas at the cathode cell in this process.

The most appropriate analysis of the electrolysis of coal is to compareit to the alternative of burning the carbon in a boiler for conventionalpower generation.

The oxidation of carbon to carbon dioxide in a boiler will generate heatas follows:C+O₂→CO₂ Ho=−393.7 KJ  (1)

The oxidation of the two moles of hydrogen will produce the followingheat (2):2H₂+O₂→2H₂O Ho=−572.0 KJ  (2)

The heat used in the electrolysis of coal (3) must be subracted from(2).C+2H₂O→CO₂+2H₂ Ho=178.3 KJ  (3)

Kordesch and Simader (p. 323) state that the theorem voltage forreaction (3) is 0.21 volts but the actual voltage is between 0.7 and 0.9volts. Based on reaction (3) requiring 4 Faradays and 1 watt-hour beingequivalent to 3,600.7 joules, the actual energy required by (3) can beestimated and deducted from the heat of reaction (2) to obtain acomparison of the heat of reaction in burning carbon to carbon dioxidein a boiler and converting the carbon to hydrogen by electrolysis andoxidizing the hydrogen for power generation. This comparison is shown onTable 3 with the hydrogen being converted to electricity either by fuelcells (75% electrical efficiency) or by a combined cycle gas turbine(56.7% electrical efficiency).

TABLE 3 Thermal and Electrical Efficiency of Coal Electrolysis -Electric Power Generation These calculations give an indication of theCommercial Thermal and Electrical Efficiency of the coal electrolysisprocess. Consider only carbon for simplicity during the electrolysis ofcoal. Assumptions of the various efficiencies are listed below. Theoverall reaction of the electrolysis of coal is: C + 2H₂O → CO₂ + 2H₂Energy Output if carbon is burned in a boiler for power generation: C +O₂ → CO₂ Ho = 393.7 KJ/Mol. Energy from 2H₂ produced from theelectrolysis of coal: C + 2H₂O → CO₂ + 2H2H₂ + O₂ → 2H₂O Ho = 572.0KJ/Mol. Energy used in electrolysis to produce 2H₂: Current to produce2H₂ gram mols = 96,484 × 4 =  385,936 coulombs = ampere secondsAmpere-hours to produce 2H₂ moles at Assumed Current Efficiency   112.85amp.-hours Theoretical Voltage of Coal Electrolysis =    0.21 voltsCurrent Efficiency in Coal Electrrolysis, %   95.00 Fuel Cell ElectricalEfficiency, %   75.00 Gas Turbine Electrical Efficiency, %   56.70Coal-Boiler-Turbine Electrical Efficiency for lignite, %   28.00Coal-Boiler-Turbine Electrical Efficiency for black coal, %   35.00 1 KJ=    1000 joules 1 watt-hour = 3,600.70 joules Theoretical conversion ofheat of oxidation of hydrogen to water to electricity is 82.9%. NOTE:The net Electrical efficiency of the Fuel Cell and Gas Turbine iscompared to Gross W-H of C to CO₂. Coal Electrolysis Gross Watt FuelCell W-H Input W-H Feed to Electri- Net W-H Production Nett W-H for Coalfor Voltage Watt- Hours of W-H for into Coal cal Plant Production FuelCell Plant Gas Turbine Plant Gross W-H Boiler Turbine System Volts Hours2H2 · 2H2O Coat Elect. Electrolysis Fuel Cell Gas Turb Net W-H ElectEff, % Net W-H Elect Eff, % C to CO2 Lignite Black Coal 0.2100 23.70158.86 31.60 133.04 127.26 127.26 95.45 87.29 72.16 65.99 109.34 30.6238.27 0.2625 29.62 158.86 39.50 138.96 119.36 119.36 89.52 81.87 67.6861.90 109.34 30.62 38.27 0.3150 35.55 158.86 47.40 144.89 111.46 111.4683.60 76.46 63.20 57.80 109.34 30.62 38.27 0.3675 41.47 158.86 55.29150.81 103.56 103.56 77.67 71.04 58.72 53.70 109.34 30.62 38.27 0.420047.40 158.80 63.19 156.74 95.66 95.66 71.75 65.62 54.24 49.61 109.3430.62 38.27 0.4725 53.32 158.86 71.09 162.66 87.76 87.76 65.82 60.2049.76 45.51 109.34 30.62 38.27 0.5250 59.24 158.86 78.99 168.58 79.8779.87 59.90 54.78 45.28 41.42 109.34 30.62 38.27 0.5775 65.17 158.8686.89 174.61 71.97 71.97 53.97 49.36 40.80 37.32 109.34 30.62 38.270.6300 71.09 158.86 94.79 180.43 64.07 64.07 48.05 43.95 36.33 33.22109.34 30.62 38.27 0.6825 77.02 158.86 102.69 186.36 56.17 56.17 42.1338.53 31.85 29.13 109.34 30.62 38.27 0.7350 82.94 158.86 110.59 192.2848.27 48.27 36.20 33.11 27.37 25.03 109.34 30.62 38.27 0.7875 88.87158.86 118.49 198.21 40.37 40.37 30.28 27.69 22.89 20.93 109.34 30.6238.27 0.8400 94.79 158.86 126.39 204.13 32.47 32.47 24.35 22.27 18.4116.64 109.34 30.62 38.27 Column A B C D E F G H I J K L M N

Table 3 shows that the thermal efficiency of the coal to hydrogenprocess depends greatly on the voltage used for electrolysis. Thevoltage for electrolysis consists of the voltage for the reaction of0.21 volts plus the over-voltage at the electrodes plus the resistancevoltage of the electrolyte between the electrodes. There is anothervoltage that may be present based on observations in our experiments. Aselectrons are withdrawn from the anode electrolyte and impressed on thecathode electrolyte, the anolyte develops a positive charge while thecatholyte develops a negative charge. Perhaps other researchers havecombined this voltage as part of the electrode over-voltage but his maybe dealt with separately. The electrode over-voltage can be reduced byusing the appropriate material and surface structure of the electrodeand high temperature and pressure. Resistance between electrodes can bereduced by using high temperature and pressure to improve conductivityand reduce the effect of gas bubbles in the electrolyte.

DESCRIPTION OF THE INVENTION

In one form therefore the invention is said to reside in n electrolyticprocess that converts solid, liquid, or gas hydrocarbon compounds andwater to carbon dioxide and hydrogen at high reaction rates using anelectrolytic cell that operates without a diaphragm at high pressure andmoderate temperature using catalysts in an electrolyte, wherein theelectrolytic cell consists of the anode cell containing an anodeelectrode connected to a DC power source and an anode solution electrodeconnected by an external conductor to a cathode solution electrode and acathode cell containing a cathode electrode connected to the DC powersource and the cathode solution electrode and an electrolyte containingthe hydrocarbon compounds is reacted with water in the anode cell toproduce carbon dioxide and hydrogen ions and the electrolyte containingthe hydrogen ions is transferred to the cathode cell and hydrogen ionsare reacted in the cathode cell to produce hydrogen.

In an alternative form the invention is said to reside in anelectrolytic apparatus that converts solid, liquid, or gas hydrocarboncompounds and water to carbon dioxide and hydrogen at high reactionrates using an electrolytic cell that operates without a diaphragm athigh pressure and moderate temperature using catalysts in theelectrolyte, characterised by the electrolytic cell including an anodecell having an anode electrode connected to a DC power source and ananode solution electrode connected by an external conductor to a cathodesolution electrode and a cathode cell containing a cathode electrodeconnected to the DC power source and the cathode solution electrode andthe anode electrode and the cathode electrode have a shape and a surfacestructure designed to achieve intimate contact with the electrolyte andthe ions contained in the electrolyte and material on the surface of theanode electrode and the cathode electrode offer low potential resistanceor over-voltage, means to supply electrolyte and hydrocarbon compound tothe anode cell and to transfer electrolyte from the anode cell to thecathode cell whereby electrolyte containing the hydrocarbon compound isreacted with water at the anode cell to produce carbon dioxide andhydrogen ions and the electrolyte containing the hydrogen ions istransferred to the cathode cell and hydrogen ions are reacted in thecathode cell to produce hydrogen.

Preferred embodiments of this invention are fully described in atechnical description and a description of the commercial process toproduce hydrogen from coal. The invention can be applied also to liquidhydrocarbon compounds in a similar fashion to coal electrolysis. Forprocessing hydrocarbon liquids in a commercial process, it is necessaryto break-up the hydrocarbon liquid into very fine particles by adding anemulsifying agent to the hydrocarbon and providing intense agitationwith the electrolyte. For a gas such as methane, the anode reactionsare:CH₄−4e(−)→C+4H(+)  (4)C+2H₂O−4e(−)→CO₂+4H(+)  (5)At the cathode:8H(+)+8e(−)→4H₂  (6)

TECHNICAL DESCRIPTION

The technical basis of this invention is shown in FIG. 1. Theelectrolyte contains the fine coal particles in suspension and thecatalyst ions such as ferrous ions. The ferrous ions are oxidised at theanode to ferric ions and the ferric ions in turn oxidise the coalparticles and water in the electrolyte to carbon dioxide and hydrogenions. The carbon dioxide is separated as a gas and the electrolytecontaining the hydrogen ions is transferred to the cathode cell wherethe hydrogen ions are reduced to hydrogen gas by the electrons suppliedby the DC power source to the cathode electrode. The hydrogen gas isremoved from the electrolyte and the neutral electrolyte is returned tothe anode cell where coal particles and water are added. The ioniccircuit of the process is achieved by transferring the electrolytecontaining the hydrogen ions from the anode to the cathode. Theelectronic circuit of the process is completed by the externallyconnected solution electrode where the electrons travel from the anodeelectrode to the DC power source to the cathode electrode through thecatholyte to the cathode solution electrode to the external conductorconnecting the solution electrodes to the anode solution electrodethrough the anolyte and to the anode electrode.

Using similar principles, the electrolysis of coal may also be carriedout using compound electrodes in the anode and cathode cell. Thecompound electrodes and the process are shown on FIG. 2. The compoundelectrodes consist of an inner electrode and an outer electrode thatacts as the anode or cathode electrode. The inner and outer electrodesare in electrical contact by means of a conducting liquid, or gel, orelectrolytic membrane. The DC power source connects to the anodeelectrode and the cathode electrode while the inner electrodes areconnected by an external conductor. The electrolyte contains thesuspended fine coal particles, water, and the catalyst ions. Thecatalyst ions are oxidized at the anode electrode and in turn oxidizethe coal particles to produce carbon dioxide and hydrogen ions. Thecarbon dioxide is separated from the electrolyte and the hydrogen ionsare transferred to the cathode cell by transferring the electrolyte. Atthe cathode cell, the hydrogen ions are reduced at the cathode electrodeto hydrogen gas. This hydrogen is separated before the electrolyte isrecycled to the anode cell. The ionic and electronic circuits of theprocess are similar to the process shown on FIG. 1.

To minimize the over-voltage and impedance of the system, the anode andcathode cells may be operated at temperatures of up to 160 degreesCelsius and pressure of up to 50 bars. The anode and cathode electrodesmay be shaped so that there is maximum intimate contact between theelectrolyte and the anode and cathode electrodes. Expanded metal shapeswith modifications are an example so that the electrolyte is in intimatecontact with the electrodes. Surface coating of the anode and cathodesolution electrode may also be selected to minimize over-voltage. Theanode solution electrode and the cathode solution electrode may bemodified so that these electrodes only act as current carriers. Theactive surfaces of the solution electrode can be covered by anon-conducting screen to minimize the contact of the ions in theelectrolyte with the solution electrodes. A non-conducting screen may bea plastic screen with suitable design openings and thickness.

The electrolyte is preferably a mixture of water and acid such assulfuric acid or phosphoric add containing multi-valent catalyst ionssuch as iron, copper, cesium, vanadium or oxidising ions such aschlorine or bromine compounds. The electrolyte may also containmodifiers such as surfactants to allow greater wetting of the electrodesurfaces and increased aerophobic properties of the electrode surface sothat gas bubbles formed on the electrode surface particularly at thecathode do not interfere with the electrolytic reaction.

The technical process is simple but additional features may beincorporated to make the process commercially viable particularly interms of the capacity, impedance, and efficiency of the commercialprocess.

Commercial Process

Concentric cylindrical cells where the anode or cathode is the outercylinder and the solution electrode is the inner cylinder may be usedfor small plants up to 5 kilowatt capacity, however, cubical cells witha centre circulating well fitted with an impeller for agitation arepreferred for large capacity electrolytic cells as shown on FIG. 3. Oneset of electrodes on either side of the circulating well is installed.At the anode cell, the electrodes will alternate between solutionelectrode and anode electrodes. Similarly, solution electrodes andcathode electrodes alternate at the cathode cell. The circulating slurryand the action of the impeller maintain the coal particles insuspension, provide good mixing of the electrolyte at the electrodesurface to minimize over-voltage, and provide good contact between thecatalyst ions in the electrolyte and the coal particles.

The electrolyte may be alkaline or acidic but the preferred electrolyteis mixtures of sulfuric acid or phosphoric acid and water. Laboratorytests have shown that the conductivity of the electrolyte increases withtemperature up to the boiling point of the electrolyte. The electrolytetemperature may be maintained at up to 160 degrees Celsius and thepressure may be maintained at up to 50 bars pressure. These conditionswill reduce the electrode over-voltage substantially and the impedanceof the electrolyte between electrodes including the effect of the gasbubbles on impedance. Modifying agents such as surfactants may also beadded to the electrolyte to improve wetting of the surface of theelectrodes. At the cathode electrode, modifying agents will make thesurface of the electrode aerophobic to separate gas bubbles from theelectrode surface faster to allow the maximum area of the cathodeelectrode available for reaction. Modifiers in the electrolyte may alsoplay a reducing role at the cathode cell similar to their oxidising roleat the anode cell.

The anode electrode may be made of expanded sheet of titanium coatedwith platinum-rhodium-iridium oxides. There may be a variety ofelectrode configuration to provide large areas for contact between theanode electrode and the electrolyte. This electrode construction isrelatively expensive and other cheaper electrode material are possible.The anode solution electrode may be made of the same material but othermaterials such as antimonial lead would be sufficient. The anodesolution electrode may also be shielded by a plastic screen to preventdirect contact of the catalyst ions with anode solution electrode toensure that the anode solution electrode functions only as an electronconductor.

The pressure is reduced after the anode cell to release the carbondioxide gas and to separate both un-reacted coal particles and insolublematerial form the electrolyte. Un-reacted coal may be recovered byflotation or gravity separation and is recycled to the anode cell.Insoluble material is discarded to the waste pond. Further steps such aswet cycloning, liquid vortex separation or applying vacuum may be usedto remove any carbon dioxide in the electrolyte. The clear electrolytecontaining the hydrogen ions is fed under pressure to the cathode cell.Temperature is at up to 160 degrees Celsius while the pressure is at upto 50 bars. The hydrogen ions are reduced to hydrogen gas at the cathodeelectrode.

The pressure of the catholyte is reduced to allow the hydrogen gas toseparate from the electrolyte. The hydrogen gas is cooled and driedbefore dispatch to storage while the catholyte is returned to the anodecell feed system where fine coal, reagent make-up and water are added.

A bleed solution may be taken to remove impurities that tend to build upin the electrolyte. Simple methods such as evaporation and cooling maybe the most effective and low cost methods. Purified electrolyte isreturned to the main circuit.

A similar process applies when compound electrodes are used in the anodeand cathode cells instead of the solution electrodes.

An alternate method of carrying out the process is to oxdize theelectrolyte only and this is mixed with the coal in a separate leachingor reaction vessel where the oxidation of the coal is carried out asshown on FIG. 4. The coal may be in a fixed bed or as an agitated slurryof fine coal. After liquid-solid-gas separation the clear anolyte ispassed to the cathode cell where the hydrogen ion is reduced to hydrogengas. This may offer benefits such as lower pressure in the anode cellsresulting in savings on capital cost.

There may be provided microwave energy into the separate leaching orreaction vessel to assist with the reactions in the separate leaching orreaction vessel. The purpose of this addition to the process is toensure a fast reaction rate during leaching and assurance that thecatalyst ions in the electrolyte are used up in the coal leaching stepto prevent the consumption of electrons by the catalyst ions at thecathode as this would lead to lower electrical efficiency of theprocess. The microwave energy may be applied at 800 to 22,000 megahertzand it may be applied at a steady state or the microwave energy may bepulsed into the coal slurry.

This process may also be applied to the treatment of coal, oil, tarsands, or oil shale that are too deep or too costly to extract byconventional mining. This method of extraction is often called solutionmining and quite often possible because of the favorable geologicalstructure that usually confines coal and oil deposits within competentstructures allowing good recovery of the electrolyte. This method isshown on FIG. 5. Although this method may not be as efficient and be ofless capacity than processing the coal at a surface plant, it is morefriendly to the environment and may offer very competitive cost for thissource of energy.

A simple diagram of the application of the process of this invention inpower generation is shown on FIG. 6 with the efficiencies based on theoxidation of carbon. The power balance in FIG. 6 should be read inconjunction with Table 3. The waste heat from the fuel cell (or gasturbine) is not included in the power balance. In the actual plants, theutilization of the waste heat would improve the thermal efficiency ofthe system. Part of the hydrogen produced from the coal electrolysis isused to generate the low voltage DC power required for the coalelectrolysis using fuel cells. This is probably more efficient thanstepping down the voltage of part of the electricity produced in themain generator for use in the coal electrolysis. The power balance inFIG. 6 is based on a coal electrolysis voltage of 0.42 volts achievingan over-all electrical efficiency (based on carbon) of 65.62 percent fora fuel cell power generator and 49.6 percent for a gas turbine.Electrical efficiencies at different coal electrolysis voltage are givenin Table 3.

The competing fossil fuels in power generation are coal and natural gas.Brown coal as mined has a heating value of 10 gigajoules per tonne andhas a cost currently of about US$2.50 per tonne at minesite. This givesa comparative cost of US$ 0.25 per gigajoule. For bituminous coal, theheat content is about 32 gigajoules per tonne and a price of about US$17per tonne at mine site. This gives a comparative cost of US$0.53 pergigajoule. The price of natural gas is about US$2.00 per gigajoule atsource. This is a general comparison as the accurate comparison is tocost fuels at the power generation site. The general comparison showsthat the coal fuel have a substantial price advantage. This priceadvantage is reduced when the cost of the coal electrolytic process toconvert the coal to hydrogen is considered. The comparative fuel cost,based on actual 56.7 electrical efficiency for natural gas in a combinedcycle gas turbine and 0.42 volts for coal electrolysis are:

Natural Gas with Combined Cycle Gas Turbine:

$\text{Fuel~~Cost~~per~~Gigajoule} = {\frac{{\$ 2}{.00}}{0.567} = {{US}\mspace{14mu}{\$ 3}{.53}}}$Brown Coal with Combined Cycle Gas Turbine:

$\text{Fuel~~Cost~~per~~Gigajoule} = {\frac{{\$ 0}{.25}}{0.4961} = {{US}\mspace{14mu}{\$ 0}{.50}}}$Black Coal with Combined Cycle Gas Turbine:

$\text{Fuel~~Cost~~per~~Gigajoule} = {\frac{{\$ 0}{.53}}{0.4961} = {{US}\mspace{14mu}{\$ 1}{.07}}}$

Table 4 provides projections of the cell sizes for commercial coal tohydrogen fuel cell power units. Table 4 is based on a coal electrolysisvoltage of 0.42 volts, current density of 3,000 amperes per square meterof active electrode surface, and cubicle cell with center circulatingwell so that the total number of electrodes is double the number shownon Table 4. The fuel cell electrical efficiency is assumed at 75percent. FIG. 7 is a diagram of a 50,000 kilowatt coal electrolyticplant. It consists of 3 cells with each cell containing 242 anodes oneach side of the center circulating well with each electrode measuring2.5 meters×35 meters active surface. The cell trains measure about 13.5meters×90 meters. Two of these cell trains will produce enough hydrogenfor a 100,000 kilowatt power plant. On the other end of the capacityscale, a 5 kilowatt unit that is suitable to provide power for a housein a developed country such as the USA will require 4 electrodes on eachside measuring 0.25 meters×0.64 meters. Cylindrical cells withtangential entry and exit of the feed stream where the outer electrodeis the anode or cathode and a concentric inner cylinder is the solutionelectrode, may be used in small capacity applications. Turbulence isachieved without the use of impellers and baffles. A 2.0 meters high by20.4 centimeters diameter cylindrical cell is equivalent to the 0.25meters×0.64 meters by 4 electrodes cubicle cell. The projecteddimensions of these commercial units will change depending on theoptimum current density and coal electrolysis voltage determined inpilot plant testing for the coal fuel used. Each coal will have optimumcharacteristics of operation including the processing of impurities.

TABLE 4 Projections of Cell Sizes for Commercial Size Coal toHydrogen-Fuel Cell Power Plants Calculations are based on CubicalCirculating Coal Slurry at the Anode Cells as shown on FIG. 8.Electrodes are plate type with alternate Anode Electrodes and SolutionElectrodes; size from .25 × .64 metres. Area of Each Cell (m²) = 300Electrodes have 2 surfaces and there are 25 electrodes each side of thecirculating center well. Fuel Cell Electrical Efficiency, % 75Theoretical Fuel cell Electrical Efficiency is 82.9%. One gram-mole ofhydrogen = joules 143000 in the reaction ½H₂ + ½O → ½H₂O(liquid) Onegram-mole of hydrogen = joules 242000 in the reaction H₂ + ½O₂ →H₂O(gas) On gram mole of hydrogen = KWH 0.03971 in the reaction ½H₂ + ½O→ ½H₂O One Gram Mole of Hydrogen Requires 96,485 Coulombs One watt-hour= Joules 3601 One Std Cubic meter of Hydrogen = moles 44.64 One grammole of hydrogen, liters 22.4 Cell Voltage for Coal Electrolysis, volts0.420 Coal Electrolysis Current Efficienty, % 95 Plant Size Current perCell No. of Cells Total Current  5 KW 7296 1 7296 100 KW 149625 1 149625 1 MW 1466325 1 1466325  10 MW 7241850 2 14483700 100 MW 24139500 6144837000 Coal Electrolytic Cell Dimensions Coal Coal Elec. Coal CoalElec Elect. Nominal Coal Electrolysis Effective Electro Power ElectrodeElectrode Number of Length Cell Current Current Prod. Power RequiredWidth Height Electrodes of Cell Electrode Density per Cell per Cell perDay meters meters in a Cell meters Area, m2 Amp/m2 Amperes KW KWH 0.250.64 4.0 0.6 3 3000 7296 3 74 0.75 1.25 14 1.8 53 3000 149625 63 15080.70 1.00 10.0 1.32 28 3000 79800 34 804 1.50 1.75 49.0 6 515 30001466325 816 14781 1.50 2.75 154.0 18.6 2541 3000 7241850 3042 72998 2.003.00 264.0 31.8 6336 3000 18057600 7584 182021 2.50 3.50 242.0 29.168470 3000 24139500 10139 243328 3.00 4.00 242.0 29.16 11816 300033105600 13904 333704 3.50 5.00 242.0 29.16 16940 3000 48279000 20277486652 Coal Elect. Fuel Cell Gross Net. Hydrogen Electricity KW KW TotalNumber Number No. of No. of No. of Produced Produced Output OutputElectrical of Cells of Cells Cells Cells Cells per Day/cell per Day perCell per Cell Efficiency Req'd Req'd Req'd Req'd Req'd gram Mols KWH KWKW % 100 MW 10 MW 1 MW 100 KW 5 KW   6533 195 8 5.04 62.21 1.0  1339863991 166 103 62.21 1.0   71459 2128 89 55 62.21 1813 181.26 18.1 16.10.6  1313059 39111 1630 1014 62.21 99 9.86 1.0 16.1 10.1  6484903 1931598048 5007 62.21 2.00 16170147 481642 20088 12484 62.21 8.01 0.80 0.116.1 124.8 21616342 643882 25828 16689 62.21 6 29645270 883010 3679222888 62.21 4 0.44 43232685 1287723 53655 33378 62.21 3 0.30

A diagram of a large commercial plant for the electrolysis of coal isshown in FIG. 8. Fine fresh coal, reclaimed coal, water, reagents, andrecycled electrolyte are mixed and preheated and then fed to each anodecell tank. There is always excess of coal to ensure maximum output fromeach anode cell. In this design, carbon dioxide is expelled from theanode cells. The reacted electrolyte and products is processed in aseries of hydro-cyclones or liquid vortex separators to separate thesolids and dissolved carbon dioxide from the electrolyte. Liquid vortexseparators are separating devices where an impeller inside a cylindercreates a vortex of the liquid or slurry fed into the cylinder. Thevortex separates the constituents of the slurry or liquid so that thelighter fraction such as gas will concentrate at the center of thecylinder and the heavy solids will concentrate towards the outer part ofthe cylinder. The fractions are separated at the conical end of thevortex separator. The liquid is then transferred to the cathode cellswhile the solids are taken to the coal separation plant where unreactedcoal is separated by froth flotation or gravity separation. Hydrogen gasis evolved at the cathode and in this design, the hydrogen is taken offthe cathode cells. The liquid is passed through liquid vortex separatorsto remove more hydrogen dissolved in the liquid before the liquid isreturned to the feed mixer. Impurities in the coal will tend to build upin the electrolyte and a bleed stream is withdrawn continuously toremove the impurities and control their concentration in theelectrolyte. Generally, the simplest method to remove impurities is toevaporate and cool the bleed solution. Metallurgical processes can beused to recover any valuable impurity in the bleed electrolyte such asnickel.

A more detailed flow diagram of a large commercial coal electrolyticplant is shown on FIG. 9. This includes the preparation of the coal andthe coal electrolytic plant. A detailed description is given below inthe Description of the Drawings.

DESCRIPTION OF THE DRAWINGS

The list of figures is:

FIG. 1 shows the principle of the electrolytic cell in coal electrolysisaccording to the present invention.

FIG. 2 shows coal electrolysis using the compound electrodes accordingto the present invention.

FIG. 3 shows circulating slurry at the anode cells using cubical celltanks according to the present invention.

FIG. 4 shows oxidation of a fixed bed or slurry of coal in a separatetank according to the present invention.

FIG. 5 shows solution mining of a deep deposit of coal according to thepresent invention.

FIG. 6 shows the power balance in a coal to hydrogen-fuel cell powerplant.

FIGS. 7A and 7B show a cross section and plan view of a large coalelectrolytic cell train according to the present invention.

FIG. 8 shows a flow diagram of a large coal electrolytic cell train.

FIG. 9 is a flow diagram of a large commercial coal electrolytic plant.

Detailed discussion of selected drawings are given as follows:

FIG. 1 shows the principle of the use of an electrolytic cell in coalelectrolysis of the present invention.

Fine coal and water 1 are continuously fed into the anode cell 2 wherethe anode electrode 3 remove electrons from the catalyst in theelectrolyte. Carbon is oxidized to carbon dioxide with hydrogen ionsproduced. Hydrogen in the coal is also converted to hydrogen ions.Carbon dioxide 7 exits the anode cell. The anode electrode 3 isconnected to the positive of the DC power source 8 while the anodesolution electrode 5 is adjacent to the anode electrode and isexternally connected by conductor 9 to the cathode solution electrode 10adjacent to the cathode electrode 12.

The anolyte 6 containing the hydrogen ions is continuously transferredto the cathode cell 11 where the cathode electrode 12 connected to thenegative of the DC power source 8 transfers electrons to the hydrogenions producing hydrogen gas 15 that is evolved from the cathode cell.Reduction reaction in the cathode cell may also be carried out throughthe use of a catalyst in the catholyte. The reacted catholyte 14containing catalysts is recycled to the anode cell 2. The electroniccircuit of the process starts from the DC power source 8 where electronsare delivered to the cathode electrode 12 then travel through thecatholyte 13 to the solution electrode 10 through the external conductor9 to the anode solution electrode 5 through the anolyte 4 to the anodeelectrode 3 and then to the DC power source 8. The ionic circuit isachieved by transferring the anolyte 4 to the cathode cell 11.

FIG. 2 shows the principle of the use of an electrolytic cell in coalelectrolysis of the present invention using compound electrodes.

Fine coal and water 15, reagents 16 including catalysts, and recycledcatholyte 32 are mixed and fed to the anode cell 17 containing thecompound electrode consisting of an outer anode electrode 18, a liquidelectrolyte or gel or electrolytic membrane 19 and an inner electrode20. Oxidation of the carbon to carbon dioxide is effected by the anodeelectrode connected to the positive of the DC power source 24 and thecatalyst in the anolyte 21. Hydrogen in the coal is converted tohydrogen ions. Carbon dioxide 22 is evolved from the anolyte while thehydrogen ions 23 are transferred to the cathode cell 26 that containsthe cathode compound electrode consisting of an outer cathode electrode27, a liquid electrolyte or gel or electrolytic membrane 28 and an innerelectrode 29. Electrons from the cathode electrode 27 connected to thenegative of the DC power source 24 reduce the hydrogen ions to hydrogengas 31 that is evolved from the catholyte 30. Reduction of the hydrogenmay also be carried out through catalysts in the catholyte. The reactedcatholyte 32 is recycled to the anode cell 17. The electronic circuit ofthe process start at the negative of the DC power source. 24 whereelectrons are transferred to the cathode electrode 27 and then travelthrough the liquid electrolyte 28 to the cathode inner electrode 29 thenthrough the external conductor 25 to the anode inner electrode 20through the liquid electrolyte 19 to the outer anode electrode 18 andthen to the positive of the DC power source 24.

FIG. 3 shows an alternative embodiment for the production of hydrogenfrom coal with a circulating slurry anode.

This description is based on the use of solution electrodes as in FIG. 1but applies also to the use of compound electrodes described in FIG. 2.Coal and water 34 is subjected to a pretreatment 35 that may includesize reduction and removal of impurities such as sodium and chlorine andinsoluble matter before the fine coal is delivered to the mixer 37 wherewater 36, reagent makeup 38 and recycled catholyte 63 are added. Theresulting feed slurry 39 is fed to the anode cell 40 containing theanode electrode 41 and anode solution electrode 42. The anode cellcontains a central circulating well 43, an impeller 45 acting againstbaffles 44 to provide agitation for the anolyte and coal slurry. Carbonin the coal is oxidized to carbon dioxide by the action of the anodeelectrode 41 and catalysts and the carbon dioxide 46 is evolved from theanode cell. Hydrogen in the coal is converted to hydrogen ions. Theanode electrode 41 is connected to the positive of the DC power source48 while the anode solution electrode 42 is connected to the cathodesolution electrode 57 by external conductor 49. The oxidized slurry 47is transferred to the gas-liquid-solid separator 50 where some morecarbon dioxide 52 is removed and the solids separated from theelectrolyte. The electrolyte 51 may further be subjected to vacuum oranother process to remove more carbon dioxide 53. The slurry isprocessed in a separator 65 to recover unreacted coal 67 to be recycledto the mixer 37 and insoluble matter to be discarded to waste. Thecarbon dioxide free anolyte 55 containing hydrogen ions is transferredto the cathode cell 56 containing the cathode solution electrode 57 andthe cathode electrode 58. The cathode cell contains a centralcirculating well 61, an impeller 46 acting against baffles 59 to provideagitation for the catholyte. The hydrogen ions are reduced to hydrogengas 62 that is evolved from the catholyte. Reduction of the hydrogenions may also be carried out by catalyst in the catholyte. The reducedcatholyte 63 is recycled to the mixer 37 after a bleed stream 64 isremoved for purification to maintain acceptable levels of impurities inthe electrolyte. The electronic circuit is the same as described in FIG.1.

FIG. 4 shows a process for the electrolytic oxidation of coal in aseparate vessel according to an alternative embodiment of the invention.

Water, make-up electrolyte, reagents 69 and reacted catholyte 99 aremixed in the mixer 71 and the electrolyte 72 fed to the anode cell 73containing the anode electrode 74 and the solution electrode 75.Agitation of the electrolyte is maintained by the circulating well 76with the baffle 76 and impeller 77. Catalyst ions in the anolyte areoxidized at the anode electrode. The anode electrode is connected to thepositive of the DC power source 80 while the anode solution electrode isconnected to the cathode solution electrode 93 by the external conductor81. The electrolyte 79 containing the oxidised catalyst ions is fed tothe leach vessel 82 containing the fixed bed of coal 83 or coal slurry.Coal 70 is fed to the leach vessel 82. Microwave energy 70 a may beintroduced into the separate reaction vessel 82 to assist with theleaching of the coal. Catalysts in the electrolyte oxidize the carbonand water to form carbon dioxide and hydrogen ion. Hydrogen in the coalis converted to hydrogen ions. The carbon dioxide 84 is evolved from theelectrolyte. Reacted coal slurry 85 is subject to gas-liquid-solidseparation 86 with the slurry 88 delivered to coal separation 89 toproduce waste product 90 and unreacted coal 91 that is recycled to theleach vessel 82. The clear electrolyte 87 containing the hydrogen ionsis fed to the cathode cell 92 containing the cathode solution electrode93 and the cathode electrode 94 connected to the negative of the DCpower source 80. Agitation of the electrolyte is maintained by a centrecirculating well 95, impeller 97 and baffles 96. Hydrogen ions arereduced to hydrogen gas at the cathode electrode. Some reduction mayalso be carried out by catalysts in the electrolyte. Hydrogen gas 98 isevolved from the catholyte before the catholyte 99 is transferred to themixer 71. A bleed solution 100 is taken for purification to control thelevel of impurities in the electrolyte. The electronic circuit is thesame as that described in FIG. 3.

FIG. 5 shows an electrolytic hydrogen process of the present inventionas applied in situ to deep deposits of coal, oil shale or tar sands.

Oxidized electrolyte is stored in vessel 104 before it is deliveredthrough waste rock 105 by pipe 106 to the broken coal deposit 107. Thecatalyst ions react with the carbon and water to form carbon dioxide andhydrogen ions. Hydrogen in the coal is converted to hydrogen ions. Deephot coal deposits provide the heat required to maintain the reaction.Except for loses, carbon dioxide and the hydrogen ions are recovered andbrought to the surface 116 with the spent electrolyte 109 throughpipeline 108. Carbon dioxide 111 is separated in vessel 110. Theelectrolyte 112 is fed to the cathode cell 113 where hydrogen gas 114 isproduced and separated. The spent electrolyte 115 is fed to the anodecell 102 where the catalyst is oxidized. The oxidized electrolyte 103 istransferred to storage 104.

FIG. 6 shows a power balance in a coal to hydrogen-fuel cell powerplant.

Coal 118 and water 119 are fed to the coal electrolysis plant 120.Inputs to coal electrolysis from a fuel cell unit 129 are DC power 121,heat 122, and water 123. Input to the fuel cell units for coalelectrolysis are air 130 and hydrogen 127 from the coal electrolysisplant 120. Another input to coal electrolysis is heat from a main fuelcell or gas turbine power plant 131 if this plant is adjacent to thecoal electrolysis plant. The output of the coal electrolysis plant 120is carbon dioxide 125 and hydrogen gas 126. Part of the hydrogenproduced 127 is fed to the fuel cell units 129 and the rest of thehydrogen 128 is fed to the main fuel cell or gas turbine power plant131. Other input to the main power plant is air 132 and the outputs arewater 133 and electric power 134. This power balance is based on a coalelectrolysis voltage of 0.42 volts and a fuel cell efficiency of 75percent.

FIG. 7 shows an embodiment of the present invention as applied to a 50MW coal electrolytic plant.

The cross section FIG. 7A shows the anode cell 135 containing the anodeelectrode 136 and the anode solution electrode 137. Agitation ismaintained through a circulating centre well 138, impeller 139, baffles140 and agitator shaft 141. The anode cell 135 may be insulated andprovided with heating cavity. The adjacent cathode cell is similar tothe anode cell structure. The cathode dimensions are shown the same asthe anode cell dimensions but the dimensions of the cathode cell andelectrodes may vary depending on the optimum current density determinedafter testing of the particular coal. The plan view FIG. 7B shows onetrain of cathode cells 148 and one train of anode cells 149.

FIG. 8 shows a large electrolytic cell train for coal electrolysisaccording to an embodiment of the present invention.

The process described is a circulating coal slurry at the anode cell.Fine coal 150, water 151 and reagents 152 are fed into the mixer 153along with reclaimed coal 170 and recycled electrolyte 167. The coalslurry 154 is heated in preheater 155 and then fed to the anode cell156. Carbon dioxide 157 is produced at the anode cell and the reactedslurry 158 containing the hydrogen ions is fed to liquid vortexseparators 159. Thick slurry 160 is dispatched to coal separation 168while some more carbon dioxide is removed from the electrolyte 161containing the hydrogen ions. This electrolyte 161 is fed to the cathodecells 162 where hydrogen 163 is produced. The spent electrolyte 164 ispassed through liquid vortex separator 165 to remove more hydrogen 166from the electrolyte before the electrolyte 167 is recycled to the mixer153. Coal separation 168 may be carried out using froth flotation orgravity separation producing waste 172 and reclaimed coal 170. Washwater 169 is added to reclaim electrolyte from the waste and this leanelectrolyte 171 joins the recycled electrolyte 167.

FIG. 9 shows a commercial plant for the electrolysis of coal accordingto an embodiment of the present invention.

Coal preparation may consist of the run-of-ne coal 176 reduced in sizeby impact crusher 177 and ground fine using a vortex grinder 178.Upgrading may be washing to remove soluble matter like sodium chlorideor removing insoluble matter by froth flotation 181 or by gravityseparation. In this example, froth flotation is described. The fine coalis slurried in tank 179 with recycled liquids 184 and 188 and the slurry180 is subjected to froth flotation where high purity coal 183 isdelivered to coal slurry storage 187. Flotation tailings 182 aresubjected to liquid vortex separation 185 with the waste 186 going topond storage. Liquid is recycled to the slurry tank 179. Filtered finecoal 190 is fed to the slurry tank 193. If the run-of-mine coal 176 isof sufficient purity, the fine coal is fed directly to the feed slurrytank 193. Acid and water 191, catalysts 192 and recycled electrolyte 223are added to the slurry tank 193 to produce coal slurry 194 that isheated in heater 195 where the heat is supplied from heat exchanger 199using heat 200 from the fuel cell plant. The heated coal slurry 194 isfed to the anode cell 196 under pressure of up to 50 bars andtemperature of up to 160 degrees Celsius with water 197 added into theanode cell 196. The reacted coal slurry 198 is kept in a reaction tank202 to complete the oxidation of the coal before the reacted slurry 203is fed into the flash tank 204 to bring the pressure to atmospheric. Thehot flash tank will help in the removal of the carbon dioxide 205 thatis cooled in cooler 209 before being stored in carbon dioxide storage211. Liquid 206 from the flash tank is passed through liquid vortexseparators 207 to remove more of the carbon dioxide 208 which is sent tothe cooler 209. Thick slurry 212 from the liquid vortex separators issubjected to washing in liquid vortex separators 215 with wash water216. The solids 217 are sent to coal recovery 186 or to waste. The weakadd wash water joins the electrolyte stream 223. If required,electrolyte 213 from the liquid vortex separators 207 may be clarifiedin pressure filters 214 before it is heated in heater 218 and fed underpressure to the cathode cell 220. The electrolyte 221 containing thehydrogen gas is flashed in tank 224 where the hydrogen gas 225 isseparated and cooled in cooler 227 before going to storage 228. Liquid223 from the flash tank and 226 from the cooler are recycled to the coalslurry tank 193.

The electrolysis of coal to produce hydrogen can be carried out in aconventional diaphragm electrolytic cell but the reaction rates are toolow that the process has no commercial value. This invention relates toa commercial process for the electrolytic conversion of coal or othersolid hydrocarbons, liquid hydrocarbons and gas hydrocarbons and waterat fast reaction rate to produce high purity hydrogen that is suitablefor electric power generation and fuel for proton electrolytic membranefuel cell powered transport vehicles. This invention was described usingcoal as the fuel because coal is the most abundant and widely dispersedof the fossil fuel with world reserves of several hundred years. Theprocess of this invention is based on an electrolytic cell that operateswithout a diaphragm and delivers high reaction rates from small to verylarge capacity plants. The process contains innovative features such asoperation under high pressure and moderate temperature and the simpleremoval of contained carbon dioxide gases from the electrolyte so thatthe hydrogen produced is not contaminated by carbon dioxide to make thehydrogen suitable fuel for proton electrolytic membrane fuel cells. Thecarbon dioxide produced in this process is of high purity suitable forindustrial use or convenient for subsequent disposal process to preventglobal warning.

There are large deposits of lignite and brown coal that contain moistureup to 66 percent that are ideal feed to the process of this inventionbecause the process requires 3 tonnes of water for one tonne of carbonin the coal. There are also a range of coals from lignite to bituminouscoal that have toxic or harmful impurities such as sulfur, mercury,arsenic, lead, cadmium and others that are not suitable as fuel forconventional commercial processes due to the interference of theimpurities with process and the equipment or the harmful effect on theatmosphere such as add rain or dispersal of heavy metals in theatmosphere. The process of this invention is capable of processing theseimpure coals and separates these impurities in the process for safedisposal.

1. An electrolytic process that converts solid, liquid, or gashydrocarbon compounds and water to carbon dioxide and hydrogen at highreaction rates comprising the step of using an electrolytic cell thatoperates without a diaphragm at high pressure and moderate temperatureusing catalysts in an electrolyte, wherein the electrolytic cellconsists of an anode cell containing an anode electrode connected to aDC power source and an anode solution electrode connected by an externalconductor to a cathode solution electrode and a cathode cell containinga cathode electrode connected to the DC power source and the cathodesolution electrode and the electrolyte containing the catalysts and thehydrocarbon compounds are reacted with the water in the anode cell toproduce the carbon dioxide and hydrogen ions and an electrolytecontaining the hydrogen ions is transferred to the cathode cell and thehydrogen ions are reacted in the cathode cell to produce the hydrogen.2. A process as in claim 1 wherein in the anode cell the anode electrodeand the anode solution electrode are formed by a compound electrodecomprising an inner anode electrode and an outer anode electrode and inthe cathode cell the cathode electrode and the cathode solutionelectrode are formed by a compound electrode comprising an inner cathodeelectrode and an outer cathode electrode with the anode inner electrodeconnected to the cathode inner electrode by the external conductor andthe outer anode electrode and the outer cathode electrode connected tothe DC power source.
 3. A process as in claim 1 wherein the hydrocarboncompounds are fine coal and the electrolyte is in the form of a slurrywhich is reacted with the water in the anode cell to produce the carbondioxide and the hydrogen ions.
 4. A process as in claim 3 wherein theslurry is preheated.
 5. A process as in claim 3 wherein the slurry fromthe anode cell is retained in a reaction vessel to allow completion ofreactions.
 6. A process as in claim 3 wherein the slurry from the anodecell is subjected to liquid-solid-gas separation using a flash tank toreduce pressure and using liquid vortex separators or hydro-cyclones toseparate the carbon dioxide, the electrolyte containing the hydrogenions, and unreacted coal with insoluble waste.
 7. A process as in claim6 wherein the slurry is processed to extract the unreacted coal forrecycle to the anode cell.
 8. A process as in claim 6 wherein theelectrolyte containing the hydrogen ions is preheated.
 9. A process asin claim 1 wherein the catalysts are selected from iron, copper, cesium,vanadium, chlorine, bromine, boron or multi-valent ions.
 10. A processas in claim 1 wherein the anode electrode and the cathode electrodeshape and surface structure are designed to achieve intimate contactwith the electrolyte and ions contained in the electrolyte.
 11. Aprocess as in claim 1 where material on the surface of the anodeelectrode and the cathode electrode offer low potential resistance orover-voltage.
 12. A process as in claim 1 wherein active surfaces of theanode solution electrode and the cathode solution electrode are shieldedby a non-conductor screen to prevent continuous contact of the catalystsin the electrolyte.
 13. A process as in claim 1 further including addingmodifiers to the electrolyte and on the surface of the anode and cathodeelectrodes so that the surface of the anode electrode and the cathodeelectrode are wetted by the electrolyte but are aerophobic or reject gasbubbles on the surface.
 14. A process as in claim 1 wherein thetemperature at the anode cell and the cathode cell is maintained at upto 160 degrees Celsius.
 15. A process as in claim 1 wherein the pressureat the anode cell and at the cathode cell are maintained at up to 50bars.
 16. A process as in claim 1 where the water in the form of steamis added to the anode cell to provide heat as well as water for an anodereaction.
 17. A process as in claim 1 wherein the anode cell and cathodecell are cubicle cells containing one set or a multitude of electrodesfor large capacity plants or concentric cylindrical cells for lowcapacity plants.
 18. A process as in claim 1 wherein the electrolyte isreduced in pressure at a flash tank to separate hydrogen gas from theelectrolyte.
 19. A process as in claim 18 wherein the electrolyte isfurther treated in a liquid vortex separator or hydro-cyclone to recovermore hydrogen.
 20. A process as in claim 1 wherein the electrolyte isrecycled to a slurry feed tank of the anode cell.
 21. A process as inclaim 1 wherein a bleed stream is taken from the electrolyte.
 22. Aprocess as in claim 1 wherein only the electrolyte is fed into the anodecell and wherein the electrolyte from the anode cell is fed into aseparate leaching vessel containing coal particles either in a fixed bedor a stirred slurry of coal particles and the electrolyte.
 23. A processas in claim 22 wherein the slurry in the separate leaching vesselcontaining the coal particles is subject to microwave energy in theseparate leaching vessel.
 24. A process as in claim 22 wherein theslurry from the separate leaching vessel is subjected to gas-liquidsolid separation.
 25. A process as in claim 22 wherein the slurry isprocessed to reclaim the coal to be recycled to the separate leachingvessel.
 26. A process as in claim 1 wherein the electrolyte containingthe hydrogen ions is preheated and transferred to the cathode cell. 27.A process as in claim 1 wherein the hydrocarbon compounds are ahydrocarbon liquid.
 28. A process as in claim 27 wherein the electrolytefurther contains an emulsifying agent is added to break up thehydrocarbon liquid into very fine particles.
 29. A process as in claim 1wherein the hydrocarbon compounds are hydrocarbon gas.